Reaction products of diketene with certain substituted n-(alkylamino) succinimides



'' 3,546,243 Ice Patented Dec. 8, 1970 United States Patent hydride are used per mole of polyamine, compounds of 3,546,243 Formula II are largely produced.

To prepare the compounds of the invention, the suc- SUCCINIMIDES cinimide may be dissolved in a suitable solvent, for ex- Keith Coupland, Hornsea, England, assignoi', by mesne 5 ample toluene, and d1kete11e addefi, p l y y, to assignments, to Orohis Limited, Piccadilly, London, the solution. A mildly exothermic reaction occurs and England, a British company when completed water is removed suitably by azeotropic No Drawing. Filed Sept. 21, 1967, Ser. No. 669,405 distillation with the solvent. The product is then isolated Claims P y, application Great Britain, 1, 1966, by removal of the solvent, suitably by distillation under 43,969/66 reduced pressure.

and 27/10 The compounds of the invention are useful as ashless 260-3263 6 Clam dispersant additives in lubricant compositions, and show improved characteristics with respect to copper corrosion when compared with certain prior art dispersant additives. Accordingly the invention further comprises lubri- ABSTRACT OF THE DISCLOSURE T invention is novel Compounds Produced y reaction cant compositions containing the novel compounds. 0 diketene With Certain alkyl or a y Substituted The invention is further illustrated by the following exrivatives of N-(alkylamino) succinimide of specified forl mula. The additives find application as lubricant addi- E l 1 tives.

A 3 litre flask was charged with compound of Formula I in which R was C polybutene and n had the value 2 The present invention relates to certain novel comand m had the value 2 (1503.5 gm.), and toluene (200 pounds and their uses, particularly their use as ashless ml.). The flask was equipped for stirring, diketene addilubricant additives. tion and removal of water via a Dean and Stark distilla- The present invention provides novel compounds protion head. The solution was warmed to C. and diduced by the reaction of diketene with a succinimide of ketene added slowly, when a mildly exothermic reaction formula took place. When the addition was complete the reaction wherein R and R are long chain alkyl or alkenyl radicals mixture was refluxed and water of reaction (8.5 ml.)

which may be the same or different, 11 is an integer having was removed via the Dean and Stark head. The product a value 2 or 3, m is an integer having a value in the range was isolated by removal of solvent under reduced pressure 0 to 8 and p and q are integers having values such that and found to contain 2.0% nitrogen.

the total (p+q) lies in the range 0 to 8.

The radicals R and R which may be the same or dif- Example 2 ferent, must be long chain radicals and may contain be- A compound of Formula I (1 mole) in which R was tween 20 and 200 Carbon atoms, Preferably between 30 derived from polyisobutene containing 70 carbon atoms, to 150. The radicals are commonly derived from polyn had the value 2 and m the value 2 was reacted with olefins such as polyethylene, olypropylene, polyblltylene diketene (2.5 moles) using the same procedure as den p lyi yl h gh the m y be derived om scribed in Example 1. The product contained 2.14% any substantially aliphatic hydrocarbon. It is particularly nitrogen,

preferred to use a succinimide of Formula I in which R, E l 3 is a 01 isobuten 1 radical havin about 70 carbon atoms in i m y g The product of Example 1 was evaluated by comparison with the compound of Formula II in which n had the value 2 and R was C a known dispersant additive for lubricating oils in a Petter Wl Oil oxidation and copper lead corrosion engine test, modified by extending the test duration from 36 to 48 hours. The additives were evaluated in a lubricant composition comprising:

The compounds of Formula I and 11 may be prepared by reaction in known manner of succinic acid or anhydride containing substituent R or R radicals with a polyamine. The polyamine may be a polymer of ethylene diamine when n has a value 2, or of 1,3-propylene diamine when n has the value 3. Suitable polymers are, for exalrln ile, tetrta- Percent ethylene pentamine, when m or (p|q) wi ave t e values 2 or 1 respectively, or tripropylene tetramine, g g i gz g zgggi g when m or (p-i-q) will have the values 1 or 0 respecrsant ugder test ry c r Xy e) 2'0 tively. When equimolar amounts of succinic acid or anpe hydride and polyamine are used, compounds of Formula In solvent-refined high viscosity index parafiinic SAE I are largely produced. When two moles of acid or an- 30 grade (a Middle East lubricating oil).

The results of the test are given in the table below. of iron octoate. Bearings are cleansed of oil, dried and weighed, then seated in the cell. The bath and coking BLE 1 panel are brought to the required temperature and oil Totalbearingl circulation started. Air is introduced via a flow meter Weight 1088, Piston merit rating and agitation begun; timing of the experiment commences Under a from the start of the air how. The onset of corrosion can Dispersmlt 361m 48 Skirt crown be accurately determined by removing the bearings at Cmpound0fFonnu1aI 227 10 8 intervals and weighing them after cleansing of oil and Product of Example 1 U. 2 13. 5 3 drying 1 Acoppervlead bear1ng 10 A bearing weight loss to correspond with acceptable 236lr-rat111g0l1t Petter W1 performance less than mg.

The results of these tests in an eight hour run are A pass result=Skirt not less than 9.5; undercrown not given in Table 2 below. less than 6.5. TABLE 2 As can be seen the pistons remain acceptable and the 15 total bearing weight loss was much reduced with the Dispersant: Bearing wt. loss (mg) novel compound. Additive A 23.5 Exmple 4 Material of Example 1 2.0 Material of Example 2 NIL The products of Examples 1 and 2 were evaluated in a a laboratory copper-lead hearing test and compared with I claim:

a known dispersant additive for lubricating oils (Additive 1. A compound produced by the reaction of diketene A) having a formula according to Formula I in which with a succinimide of formula R1 /CO N[(CH2) nNH](CH .,NH(oI-I NI-I 2 m Rr\ /C O\ 00 119 CH \CH/ E Z)H 2)H Z)n 2)n 2)D I H2 q CII2 oo 00 ll R was C and n and m had the values 2. The additives wherein R and R are long chain alkyl or alkenyl radicals were evaluated in a lubricant composition comprising: which may be the same or different and which contain between 20 and 200 carbon atoms, n is an integer having a Percent val e 2 3 i t h 1 th Zinc dialkyl dithiophosphate 0.5 O 8 3; 3;; an if a Va m Basic detergent additive (metal aryl carboxylate) 3.0 p q 1 egers avmg Va ues i a K the total (p-l-q) lies in the range 0 to 8, the reaction being Dispersant 2.0

v carried out 1n the presence of a solvent for said sucin solvent-refined high viscosity lndex paraffimc SAE 30 i i id grade mineral oil. 2. Compound according to claim 1 wherein the radi- The test is carried out 1n apparatus whlch conslsts of a gals R d R are h same, gl 0611, Fq -lPP W a stiffen SUIT 1S q pP 3. Compound according to claim 1 wherein the radicals with a cylindrical mild steel rotor whlch clears the bear- R d R are d i d f o ol th l ol l ings whose corrosion is being measured, but provides sufiiolybutylene and polyisobutylene. cient oil shear at the bearing surface to remove deposits. 4, C nd according t lai 1 produced b th The glass cell has Provision for air fi?" Outlet, P reaction of diketene with a succinimide of Formula I in circulation outlet and a side tube containing the coking hich R is a polyisobutenyl radical having 70 carbon panel and mounting. The coking panel mountlng 1S drilled atoms i the side chain to take a heating element, res1stance thermometer and 5 compound according to Claim 1 .Whemin the integer thermocouple. Copper-lead bearings, of the type used m has the value 1 or 2' in the Petter W1 test engine, are seated in the lower c ound accordin to claim 1 wherein the total portion of the cell which is designed to hold them firmly. (p+q) g the value 1 f The test cell is immersed in an oil bath, the temperature of which can be controlled at the desired bulk oil tem- Ref Cited perature. Coking panel temperatures are controlled by a resistance thermometer operating an electronic relay, the UNITED STATES PATENTS temperature of the panel being determined by the thermo- 3,444,170 5/ 1969 Norman 6t couple. Oil is fed over the coking panel from the cell by a micropump and returned to the cell. Stirring is held con- NICHOLAS RIZZO Primary Examiner stant at the required rate by controlling the motor volt- I. A. NARCAVAGE, Assistant Examiner age. Visual indication may be made using a simple tachometer device. All temperatures are recorded continuously US. Cl. X.R.

on an electrically driven potentiometric recorder. 252-51.5

The oil under test is charged to the cell with 0.025% 

